Aminoalkohole, 2. Mitt.: Ein Verfahren zur Herstellung enantiomerenreiner pharmakologisch aktiver β-Aminoalkohole

Zusammenfassung Die Reduktion enantiomerenreiner O-MBF- bzw. O-MBE-geschützter Cyanhydrine mit LiAlH₄ führt unter Einhaltung definierter Reaktionsbedingungen zu den entsprechenden geschützten Aminoalkoholen, in denen der Anteil der durch Epimerisierung gebildeten Nebenprodukte kleiner als 3% ist. Die Abtrennung der unerwünschten Diastereomere erfolgt im Zuge der Reinigung der Produkte. Durch Schutzgruppenabspaltung mit Salzsäure/Methanol können die enantiomerenreinen Aminoalkohole erhalten werden. Die meist sehr guten Trennfaktoren der O-MBF- bzw. O-MBE-geschützten Verbindungen erlauben für viele Verbindungen sowohl im Cyanhydrin- als auch im Aminoalkoholstadium eine präparative Trennung und machen das Verfahren deshalb vielseitig verwendbar.

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Aminoalcohols II: Preparation of enantiomerically pure pharmacologically active -aminoalcohols

Summary A synthesis of -aminoalcohols is described starting from racemic or enantiomerically pure -hydroxynitriles which were O-protected using enantiomerically pure acetal type protective groups. Reduction with lithium aluminium hydride yielded O-protected -aminoalcohols. Whenever diastereomeric O-protected cyanohydrins could not be separated, the mixture was reduced and the resulting O-protected aminoalcohols were separated. Removal of the protective group using hydrogen chloride and methanol yielded enantiomerically pure -aminoalcohols or their corresponding hydrochlorides.

Herrn Prof. Dr.F. Eiden zum 70. Geburtstag gewidmet     

Self-assembly of rod-coil molecules into molecular length-dependent organization

A series of rod-coil molecules (n-x, where n represents the number of repeating units in a PPO coil and x the number of phenyl groups in a rod segment) with variation in the molecular length, but an identical rod to coil volume ratio was synthesized, and their self-assembling behavior was investigated by using DSC and X-ray scatterings. The molecule with a short rod-coil molecule (16-4) shows a 3-D tetragonal structure based on a body-centered symmetry of the discrete bundles in addition to a lamellar structure. This 3-D lattice, on heating, collapses to generate a disordered micellar structure. Remarkably, the molecules based on longer molecular length (21-5 and 24-6) were observed to self-organize into, on heating, lamellar, tetagonally perforated lamellar, 2-D hexagonal columnar and finally disordered micellar structures. Further increase in the molecular length as in the case of 29-7 and 32-8 induces a 3-D hexagonally perforated lamellar structure as an intermediate structure between the lamellar and tetragonally perforated lamellar structures. Consequently, these systems demonstrate the ability to regulate the domain nanostructure, from 2-dimensionally continuous layers, long strips to discrete bundles via periodic perforated layers by small changes in the molecular length, at an identical rod-to-coil volume fraction.     

Improved synthesis of the enantiomers of propafenone using chiral building blocks

Summary A short and efficient synthesis of the enantiomers of the antiarrhythmic drug propafenone (1) is described using both (R)-isopropylideneglycerol tosylate and (S)-glycidyl tosylate as chiral building blocks. The key step of the high yield synthesis is the acetalization of the carbonyl group in 1-(2-hydroxyphenyl)-3-phenyl-1-propanone (2) which allows application of mild reaction conditions in the subsequent alkylation of the phenolic hydroxy group.With our best wishes dedicated to Prof. Dr.H. Achenbach on the occasion of his 65^th birthday     

Organization of branched rod-coil molecules into a 3-D tetragonally perforated lamellar mesophase

Tetramerization of coil-rod-coil ABC triblock copolymers to a tetrabranched molecule induces an unusual 3-D tetragonally perforated layered liquid crystalline phase as an intermediate structure between 1-D lamellar and 2-D hexagonal columnar phases.     

Determination of arsenic in some Myanmar indigenous medicines by neutron activation analysis

Am(Be) neutron source was used for activation of samples and⁷⁶As radioactivity measured by both ^– and -counting techniques. The samples analyzed were raw materials traditionally used in formulating Myanmar indigenous medicines. The results were compared with those obtained by volumetric analysis and those reported in the literature.     

Ionic impurity control by a photopolymerisation process of reactive mesogen

Extremely low ion density, 10^?8?10^?11 molar fraction, which inevitably exists due to residual ion impurities even in a purified liquid crystal (LC) compound, can significantly influence the electro-optic response in LC devices. We found that the density of ionic molecules increased with the addition of various dopants including triphenylphosphine oxide (TPPO), molecules with the functional group of aldehyde, epoxide and so on into a nematic LC cell by observing the electrical response of the LC cells and that the irradiation of ultraviolet (UV) light accelerated the generation of ionic molecules, indicating degradation of organic materials. However, the addition of reactive mesogen (RM) compounds to the LC mixture significantly decreased the effective density of ions during and after the photopolymerisation process. The cured RM networks effectively captured the ion impurities during the photopolymerising process and their ion capturing ability was sustained even after completing the photopolymerisation process. This observation may provide a simple and useful way to control the effective ion density in a liquid medium down to extremely low levels.     

Synthesis and liquid crystalline properties of T-shaped dimesogenic compounds

Two series of new dimesogenic liquid crystalline compounds were synthesized and their LC and other thermal properties were characterized. These compounds consist of two mesogenic units connected through polymethylene spacer of varying length in the shape of the letter ‘T’. The difference between the two series is in the structure of tail groups attached on the pendant azobenzene mesogens; one of which is n-butyl and the other is phenyl. The compounds were characterized for their liquid crystallinity by the differential scanning calorimetry (DSC), X-ray diffractometry and visual observation of the melts on a hot-stage attached to a polarizing microscope. All these compounds were found to form only the nematic phase enantiotropically.     

Linearization of a class of non-linear systems modelled by multibond graphs

Based on non-linear systems described by multibond graphs, a procedure designed to present symbolic linearization of these multibond graphs, is presented in this paper. Firstly, a junction structure of a multibond graph with multiport gyrators that represent Eulerian junction structures is proposed. In addition, non-linear multiport resistors are considered. By knowing the non-linear causal paths and loops of the non-linear multibond graph, the linearization is obtained by two steps: (1) The original multibond graph on the nominal operating point is evaluated; (2) New and additional paths based on the non-linear causal paths and loops are included. The state space representation of the linearized multibond graph using the corresponding junction structure is presented. An advantage of this methodology is its ability to allow the user to define a nominal operating point in which the linearization will be carried out.

In order to apply the proposed methodology, two physical systems are modelled and linearized by multibond graphs: a synchronous generator and a two degrees of freedom PUMA. Simulation results of these non-linear and linearized systems are shown.     

Temperature‐dependent location of a weakly segregated block copolymer in binary blends of block copolymers

The phase behaviors of binary blends of poly(styrene‐b‐butadiene) block copolymers were investigated by a small‐angle X‐ray scattering technique. The blends were composed of weakly segregated one in a random micellar phase and the other in a cylindrical phase with similar molecular weights and complementary volume fractions. Morphologies, domain spacings, and order–disorder transition temperatures of the blends indicated that the junctions of the constituent block copolymers share the interface at low temperatures. The domain spacing decreased as temperature increased in a blend with a small amount of the weakly segregated block copolymer. In the cases of the blends with a large amount of the weakly segregated constituent, domain spacing increased with increasing temperature. These results implied that some of the weakly segregated block copolymer moved from the interface to one microdomain at higher temperatures. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 470–476